Conversion of hydrocarbons



Oct. 26, 1943.

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Patented Oct. .26,I 1 943 f UNITED sm'rssl PATENT OFFICE Gustav Egloff, Chicago, Ill., assignor-to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware I Application May 27, 1940, Serial No. 337,359

- r 2 Claims. (Cl. 196-52) Thisinvention relates to a process for converting hydrocarbon oil into substantial yields of high antiknock gasoline. More particularly it relates to cracking hydrocarbon distillates in the y presence of a powdered crackingcatalystunder conditions adequate to produce high antiknock gasoline. v

In one'specific embodiment thepresent invention comprises mixing a hydrocarbon oil with a powdered cracking catalyst, heating the mixture at cracking conditions of temperature and pressure,'s eparately heating recycle oil and/or process gases in the presence of an additional portion of said cracking catalyst, mixing the reactants with those from the first step, adding thereto an additional quantity of powdered cracking catalyst, passing the mixture to a reaction zone followed by a vaporizing zone, recovering gasoline, gasand recycle oil, and returning a portion of .the recycle oil and gas as previously described. f

The invention is further understood by ref4 to 1000 pounds per square inch. Catalyst pow- 1 der as such or in the form of a slurry in a part of the charge or,.. a fraction of reaction products or other suitable carrier, is introduced from catalyst charger I through line 8 containing valve 9, 'pump I0, valve II and valve II', mixing with the charging stock in line I; 'The mixture passes from coil 5 through line I2 and valve I3 to reaction chamber I4. An additional quantity of the catalytic agent isintroduced through line I5 containing valve I6. The reaction products in line I2 are commingled with recycle oil and/or process gases from coil 43 whereby the temperature maybe increased if desired by heating the incoming hydrocarbons to a higher temperature than is used in coil V5. Alternatively, colder oil from line 49 may be introduced to regulate the temperature of the combined reactants, when, for example, it is desired to continue` the conversion in reactor I4 at a lower temperature than in the cracking coils. This permitsgreat ilexigasoline for .use in motor fuelsl or as aviation f bility to the process from an operating-standpoint. The reaction mixture from chamber I 4 passes through line II and valve I8 to vaporizing chamber I9. Residual oil containing catalyst in suspension is removed through line and valve 2|. A vapprous fraction is passed through line 22 and valve 2 3 to fractionator 24 from which gasoline and gas` are removed through line 25, valve 26, condenser -2'I and valve 28 to receiver 29. Gasoline is recovered through line and valve 3l, being passed to a suitable stabilizer not shown. A portion of the process gases may bc withdrawn through line 32 and valve 33. The

process gases may be further treated by vpolymerization and/or alkylation processes to produce additional yields of gasoline. A part of the receiver gases may he passed through line 34 containing valve 35, pump 36 and valve 3l to line 38 wherein they may be commingled with a Llo light recycle oil from line 39 containing valve 40, pump 4I and valve 42. The mixture passes through line 38 to coil 43 which isA disposed in heater 44. The mixture maybe heated to crack-- ing conditions of temperature and pressure of theorder o f approximately 800-1200 F. and

passed through line and valve 46, joining with line I2 .and mixing with the reactants therein as previously described. Alternatively, an additional quantity of catalyst maybe introduced through line 41 and valve 48.

As a further alternative, the gas alone may be passed through coilY 43 as described andpart or all of the reflux may be passed through-line 49 and v alve 50 to line I2 where it acts as a4 quench and thus serves asa means of decreas-v ing-the temperature of the reaction products to a `desired point. This may be done when it is desired to bring the temperature within the range of approximately 50o-850 F. under which conditions the fresh catalyst added from line I5 serves togbrin'g about the conversion of oleI-ln hydrocarbons' in the gasoline so that the nnished gasoline may be substantially olen-free.

yWhen operating in this way, .the temperatures, maintained in coils 5 and 43 are normally in excess of approximately 900 F, whereby an olefincontaining gasoline o f high antiknock value is produced. Higher boiling fractionator bottoms may be withdrawn from fractionator 24 through line 5I and valve 52 to be further cracked or to be used as ,a fuel oil.

'I'he catalytic agents employed in the present processare preferably-those known as silicaalumina, silica-zirconia and silica-alumina-zirponia. This type of catalytic lagent is prepared by the separate or simultaneous precipitation of the components under conditions such that a powdered material of particle size approaching colloidal dimensions is produced. The material is washed until substantially free of alkali metal ions and may be dried prior to introduction into the system. The catalyst may be introduced as a dry powder or as a slurry in a. part of the oil undergoing conversion, or in a part of the reaction products or any other suitable carrying medium. The quantity of catalyst used may vary from approximately 0.1-20% by Weight of the oil and is normally within the range of approximately 0.5-% of the oil. The catalyst may be recovered and reactivated by treatment with an oxygen-containing gas under conditions such that the carbonaceous and hydrocarbonaceous deposits are burned'. The temperature of reactivation should be kept ata point below 1500 F. `and preferably below 1200 F.

The following examples are given to illustrate the practicability of the invention but should not be construed as limiting it to the exact conditions given therein.

Ezra'mple I 'A Mid-.Continent gas oil may be, converted in the manner described using a silica-alumina powder employing a temperature in the gas oil conversion step of approximately 1000 F. and atemperature of-1100/ F. in the gas -conversion coil 43. No recycle oil or catalyst is employed in coil A3. Sufficient side cut maybe added to the combined feed'line I2 so that a temperature of approximately 750 F. is maintained in the reaction chamber. Approximately 1% of catalyst by Weight of the charging stock is used, half of .this

being introduced' into the combined feed line by way of line I5. A total yield of approximately 68% of '78 octane number gasoline substantially free of olefin hydrocarbons may be obtained in this manner.

' Example II to 7 pounds Reid vapor pressure andpolymerizing the olens in the stabilizer gases, an addi tional quantity of gasoline of 83 octane number may be obtained.

I claim as my invention:

1. A process for the conversion of hydrocarbon oil which comprises adding fresh powdered siliceous cracking catalyst to said oil,passingthe mixture in a confined stream through a heating zone and therein heating the same to a cracking temperature, commingling additional fresh powdered siliceous cracking catalyst with the stream of reaction products leaving said heating zone, supplying the resulting mixture to a reaction zone and therein continuing the conversion, separating cracked vaporous and non-vaporous residue containing the powdered catalyst from the resultant conversion products, fractionating said cracked vapors to separate therefrom as reux condensate fractions higher 'boiling than gasoline, cooling and condensing the fractionated vapors, separating normally gaseous materials from the resulting distillate, adding additional fresh powdered catalyst to at least a portion of the normally gaseous materials, heating the mixture of gases and catalyst to conversion temperature and introducing the heated mixture into said reaction zone.

2. A process for the conversion of hydrocarbon oil, which comprises adding a fresh powdered -siliceous cracking catalyst to said hydrocarbon oil, passingl the mixture in a confined stream through a heating zene and therein heating the same to a cracking temperature, commingling additional fresh powdered siliceous cracking catalyst with the stream of reaction products leaving said heating zone, supplying the resulting mixture to a reaction chamber and therein maintaining the same at cracking temperature, separating non-vaporous liquid residue containing the powdered catalyst. from cracked vapors, fractionating the cracked vapors to separate as reflux condensate fractions higher boiling than gasoline, separately heating said reflux condensate to a conversion temperature and subjecting the same to further conversion in said reaction chamber, cooling and condensing the fractionatedl vapors, separating normally gaseous hydrocarbons from distillate, combining fresh catalyst with said normally gaseous hydrocarbons and subjecting thel mixture to heating with said reflux condensate. GUSTAV EGLOFF. 

